EP1880028B1 - Method for recovering metals from waste and other materials comprising organic components - Google Patents

Method for recovering metals from waste and other materials comprising organic components Download PDF

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Publication number
EP1880028B1
EP1880028B1 EP06724542.3A EP06724542A EP1880028B1 EP 1880028 B1 EP1880028 B1 EP 1880028B1 EP 06724542 A EP06724542 A EP 06724542A EP 1880028 B1 EP1880028 B1 EP 1880028B1
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European Patent Office
Prior art keywords
metal
tube furnace
rotary tube
process according
rotary
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EP06724542.3A
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German (de)
French (fr)
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EP1880028A1 (en
EP1880028B8 (en
Inventor
Joachim Beyer
Walter Leidinger
Wolfgang Calaminus
Egidius Vickus
Wilhelm Kuckelsberg
Mark MÄTSCHKE
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Currenta GmbH and Co OHG
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Bayer Industry Services GmbH and Co OHG
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Priority to PL06724542T priority Critical patent/PL1880028T3/en
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/008Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases cleaning gases
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001Dry processes
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B7/00Rotary-drum furnaces, i.e. horizontal or slightly inclined
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/005Preliminary treatment of scrap
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the invention relates to a method for the recovery of metals, in particular precious metals from waste and / or materials, wherein the waste and / or materials in a preferably continuous process by thermal treatment in a process chamber, the organic components are removed and oxidized, and a plant for implementation of the procedure.
  • DE-A 9320018 and DE A 3518725 C2 is a method for thermal treatment of electronic scrap by pyrolysis known. In these processes, the pyrolysis coke remaining in the residue is removed as part of a further treatment. Partly high concentrations of dioxins and furans are expected in this pyrolysis coke.
  • DE-A 9320018 and DE A 3518725 C2 are concerned with a process for the thermal recycling of metallic objects mixed or coated with organic substances or similarly contaminated, such as paint or oil cans or cans, barrels or other containers. These starting components to be designated as scrap are introduced into a smoldering chamber in which they are first of all thermally treated without supplying oxygen.
  • This carbonization chamber is operated during the carbonization phase at a temperature in the range of about 250 to 500 ° C, heated from the outside and has a rotating drum, which is operated during the process at a rotational speed of 1 to 2 revolutions per minute.
  • flammable pyrolysis gases or combustible pyrolysis oils are produced, which can be used to bring the smoldering chamber up to temperature.
  • the smoldering process is followed by an oxidation process in which, in the same chamber, however, the pyrolysis gases generated during the smoldering process are subsequently burnt in by the introduction of oxygen. The latter can also be done in a Nachbrennhunt downstream of the smoldering chamber.
  • This document is also concerned with the recycling of precious metal dust containing rubbish as it may arise, inter alia, in the jewelry industry.
  • the invention is therefore based on the object to provide a simple method with which from metal-containing starting materials, in particular electronic waste, a secondary raw material in high yields (> 90%) is achieved.
  • the invention relates to a method for the recovery of metals from metal-containing wastes and materials, characterized in that the metal-containing waste is preferably introduced continuously into a process chamber, is thermally treated under continuous intensive mixing, the organic components are continuously removed and then oxidized and the metal-containing components, preferably as metal conglomerates and the other inorganic non-metal-containing components, are discharged substantially continuously from the process chamber.
  • Metal-containing wastes and materials in the context of the invention are usually mixtures of metals including precious metals and organic or inorganic substances.
  • the method is suitable for electronic scrap and is particularly useful for preparing for the recovery of metals such as metals. Copper, zinc, tin, lead and in particular the preparation for the recovery of precious metals, e.g. Gold, silver, platinum and palladium.
  • Examples of material to be treated are printed circuit boards equipped with electronic components or parts of devices or complete electronic devices.
  • Organic ingredients are z. As plastics, incl. Flame retardant and / or bromine, chlorine, or other halogen-containing material may be mixed with non-metallic constituents such as glass fibers. These wastes are preferably fed into the process chamber in pre-shredded form.
  • the process does not take place in consecutive process steps, possibly separated from one another by waiting pauses, in batch operation in a process chamber to be charged before the process and to be emptied again after the process, but in a continuous process.
  • the metal-containing waste is continuously fed to the process and thoroughly mixed in the process chamber.
  • US-A-3,817,697 discloses a reductive process (pyrolysis) for de-oiling metal shavings in which no coolant is added to the process chamber for temperature control.
  • US-A-4,415,360 describes a reductive process for recovering metals from wastes such as electronic scrap by thermal treatment in a Kaldo combustor, optionally also oxygen in substoichiometric ratios and / or oil can be supplied (page 5 lines 35 to 49).
  • US2005 / 0077658A1 relates to a system for treating vapors from metal recovery furnaces. US2005 / 0077658A1 does not refer to the use of thermal processes on metal-containing waste itself, but first describes the treatment of vapors arising from the thermal treatment of metal-containing waste.
  • Pankratz, E .: "Processing of spent Ni-fat catalysts" FAT SCI. TECHNOL., Vol. 95, July 1993 (1993-07), pages 487-490 and Pankratz, E .: “Environmentally friendly processing of Ni-containing catalysts” FAT SCI. TECHNOL., Vol. 97, June 1995 (1995-06), pages 508-512 ) relate to a process for the recovery of Ni-containing wastes (fatty catalysts) by oxidative combustion in a rotary kiln.
  • US-A-5 013 533 relates to a process for the recovery of metals from spent catalysts. Also in this method, a rotary kiln (22) is used in the air (18) can be flowed. Oxidative combustion takes place at temperatures of 177 ° C to 870 ° C. All of these methods have the disadvantage that more than 10% of the metal from the scrap is not recyclable and it is about sequential processes.
  • the invention is therefore based on the object to provide a simple method with which from metal-containing starting materials, in particular electronic waste, a secondary raw material in high yields (> 90%) is achieved.
  • the invention relates to a method for the recovery of metals from metal-containing waste and materials in which the metal-containing waste is preferably introduced continuously into a process chamber, is thermally treated under continuous intensive mixing and treated under supply of oxygen-containing gases, the volatile residual organic components continuously removed and then oxidized and the metal-containing components, preferably as metal conglomerates and the others inorganic non-metal-containing components, are discharged substantially continuously from the process chamber, characterized in that the combustion temperature in the process chamber by means of temperature detection means, temperature control means and a temperature control means of adding coolant into the process chamber, in a range of 400 to 1100 ° C is maintained.
  • Metal-containing wastes and materials in the context of the invention are usually mixtures of metals including precious metals and organic or inorganic substances.
  • the method is suitable for electronic scrap and is particularly useful for preparing for the recovery of metals such as metals. Copper, zinc, tin, lead and in particular the preparation for the recovery of precious metals, e.g. Gold, silver, platinum and palladium.
  • Examples of material to be treated are printed circuit boards equipped with electronic components or parts of devices or complete electronic devices.
  • Organic ingredients are z. As plastics, incl. Flame retardant and / or bromine, chlorine, or other halogen-containing material may be mixed with non-metallic constituents such as glass fibers. These wastes are preferably fed into the process chamber in pre-shredded form.
  • the process does not take place in consecutive process steps, possibly separated from one another by waiting pauses, in batch operation in a process chamber to be charged before the process and to be emptied again after the process, but in a continuous process.
  • the metal-containing waste is continuously fed to the process and thoroughly mixed in the process chamber.
  • Intensive mixing in the sense of the invention means that the waste is constantly kept in motion by means of a rotary tube, a grate furnace or in a fluidized bed process, or is introduced finely distributed in the process chamber.
  • thermal treatment is meant that in the process chamber temperatures of 400 to 1100 ° C, preferably 600 to 900 ° C, in another preferred embodiment 500 to 900 ° C, particularly preferably 700 to 850 ° C ( Fig. 2b , Phase B).
  • gases such as oxygen-containing gases, may be selectively supplied to the process chamber.
  • the process chamber is preferably formed by a rotary kiln, which essentially consists of an elongated rotary tube, which forms a feed opening on one side.
  • a rotary kiln which essentially consists of an elongated rotary tube, which forms a feed opening on one side.
  • the material lying in the process chamber, in particular in the rotary tube is thermally treated in a combustion zone B adjoining the heating zone A within a predetermined temperature range ( Fig. 2b ).
  • On the supply side can also be provided a support firing to initiate or support the thermal processes.
  • the heating of the scrap to 700 to 850 ° C by a Stütz85ung (3) which is located on the feed side (1 ') of the rotary kiln (1), initiated.
  • the process temperature is maintained within a suitable range with suitable temperature sensing means (such as a thermocouple, infrared camera), temperature control means (such as electronic image analysis of infrared camera data) and temperature control means (such as adding coolants to the process chamber).
  • suitable temperature sensing means such as a thermocouple, infrared camera
  • temperature control means such as electronic image analysis of infrared camera data
  • temperature control means such as adding coolants to the process chamber.
  • the infrared camera (5) is associated with the outlet side (1 ") and in particular with a wall spaced from the end of the rotary tube of a secondary combustion chamber (7).
  • the organic components escape in the combustion zone; the non-volatile combustion product remains at the bottom of the process chamber or rotary tube and is fed to the exit side, where it emerges as a residue containing essentially only metal components and inorganic non-metal constituents, which are fed to a subsequent processing (eg smelting) ,
  • the metal-containing waste is transported from the feed side (1 ') to the discharge side (1 "), the waste initially being heated in a heating zone (A). optionally with the aid of a support fire (3) is heated, then in an adjoining combustion zone (B), the organic components of the metallic components thermally separated and at least partially preferably mostly burned and finally the non-volatile metal components together with any non-volatile inorganic Constituents on the feed side of the process chamber opposite outlet side substantially continuously emerge.
  • the thermally separated organic components are transported away as flue gas (II), whereby a not inconsiderable amount of the organic constituents within the combustion zone is oxidized. These combustion products are contained in the flue gas (II).
  • flue gas (II) may also be metal vapors and possibly formed in the process chamber metal compounds.
  • the process management within the process chamber is preferably selected (see above) such that the proportion of the metal entering the flue gas purification as gas or as particles is below 7%, preferably below 3%, particularly preferably below 1%, of the metals to be utilized. lies.
  • Metals such as B. Al, Mg, Sb, As, which can interfere with a downstream treatment process can be removed at least partially via the flue gas (II).
  • the residence time of the flue gas in the hot zone of the afterburner is between 2 and 7 seconds.
  • the burnt flue gases separate out dusts when flowing through the downstream steam boiler (8). These collected in a dust chamber (9).
  • the components leaving the process chamber consist in particular of flue gases of combustion already carried out, incompletely oxidized organic compounds, metal vapors, compounds, dusts and other inorganic compounds. These are fed to a subsequent combustion chamber of the process chamber, in which the complete oxidation of all residual organic compounds still contained.
  • the residence time of the flue gas (II) in the secondary combustion chamber with preferably> 2 s is sufficiently large.
  • the temperature within the afterburning chamber is sufficiently high and is in particular above 850 ° C., preferably above 1000 ° C., in a further embodiment in particular above 800 ° C., preferably above 900 ° C. At such temperatures, dioxins and furans are completely destroyed.
  • the laden with inorganic pollutants flue gas (II) is then cleaned in several stages to maintain low emissions.
  • the flue gas (II) can be removed by cooling heat energy, which can be used in a suitable form elsewhere.
  • the subsequent flue gas cleaning is carried out as follows:
  • the flue gas (II) is in the first step in a so-called quenches (10) on a Temperature below 100 ° C, preferably to about 70 to 80 ° C, preferably by injection of water, cooled.
  • the quencher is followed by scrubbers to remove further components from the flue gas (II). These are rotary scrubbers that are operated acid and / or alkaline.
  • the fine dust is removed in a condensation electric filter (14).
  • the concentration of possibly present in the flue gas dioxins and furans and nitrogen oxides on a catalyst is significantly reduced.
  • the remaining value metal fractions contained in the waste water of the flue gas cleaning can be recycled via a downstream wastewater treatment plant.
  • the cleaned exhaust air is preferably discharged through a chimney (16).
  • the process is stirred so that it comes in the context of thermal treatment to melting individual low-melting metal components, which in turn solve higher melting metals.
  • this metal solution also includes precious metal components.
  • These metal components are found again in the form of metal conglomerates in the discharged residue.
  • the metal conglomerates can be separated.
  • the formation of these metal conglomerates can be enhanced by a corresponding concentration of iron and / or solders (e.g., tin, lead, bismuth).
  • iron, solders and / or flux can also be added.
  • the advantage of the invention is that the metal conglomerates can be easily separated from the solid inorganic constituents and can be added directly to a very late step of the smelting process in a subsequent treatment process (eg smelting). This can increase the efficiency of metal recovery in the downstream treatment process.
  • Another object of the invention is a plant for the thermal treatment of metal-containing wastes and materials, comprising a rotary kiln (1), a continuously operating charging device (6), adekaruchabelanze (4) from the feed side (1 ') forth in the rotary kiln (1 ), at least one afterburner chamber, at least one waste heat boiler, at least one quencher, a rotary scrubber or at least two successive rotary scrubbers, at least one condensation electrostatic precipitator and at least one post catalytic purification for the flue gases.
  • the rotary kiln (1) consists of an elongated tube, which is preferably 10 to 13 m long for industrial applications, whereby other common lengths are realized can.
  • This tube is preferably inclined relative to the horizontal and lined with a refractory material.
  • adeffenzaanze (4) is installed, which protrudes from the feed side (1 ') forth in the rotary kiln (1) and from the nozzle (4') water, a coolant is placed in the oven.
  • the temperature within the rotary kiln (1) is monitored with a thermocouple and an infrared camera (5).
  • the organic constituents are preferably removed from the scrap and the combustion products, together with any metal vapors, metal compounds and dusts which may be formed, are fed as flue gas (II) to the afterburner chamber (7).
  • the apparatus for carrying out the method consists essentially of a rotary kiln (1), which consists of an elongated tube of about 10 to 13 m. This tube is inclined relative to the horizontal and lined with a refractory material. The inclination and rotation of the tube at 10 to 20 revolutions per hour [Uph] about its longitudinal axis cause the metal-containing waste continuously introduced on the feed side 1 'via a feed device (6) into the rotary tube to pass through the tube In this case, the metal-containing waste (17) to be treated is kept constantly in motion in the rotary tube (1) and intensively mixed.
  • the rotary tube On the feed side (1 '), the rotary tube is charged with the electronic waste to be treated. This passes through the rotary tube in a time of about 1.5 hours. Larger parts of the electronic waste, such. As chassis, which consist of metal, especially iron and plastic, can be crushed and shredded in particular.
  • this scrap Due to the rotation of the rotary tube, this scrap first passes through the heating phase designated A within the rotary kiln (1).
  • a Stütz85ung (3) which is located on the feed side (1 ') of the rotary kiln (1), the heat required for the heating of the scrap heat is introduced into the rotary kiln, this is done for example with the elongated and the reference numeral (18). designated flame.
  • cooling may be required to maintain the combustion temperature in the most preferred range between 700 to 850 ° C. This temperature range should be kept in the combustion zone designated B.
  • adeffenzugabelanze (4) is provided which projects in the embodiment of the feed side (1 ') forth in the rotary kiln (1) and from the nozzle (4') water or a similar suitable coolant is placed in the oven.
  • the metal-containing waste (17) to be treated which moves on the bottom of the rotary tube from the feed side (1 ') to the outlet side (1 ") thus becomes the desired one Temperature range maintained in which the oxidation of the organic components in the metal-containing waste is achieved as completely as possible. At the same time, however, the temperature should not become too high in order to avoid that significant quantities of the metallic components to be recovered are removed via the flue gas (II). Metals such as B. Al, Mg, Sb, As, which can interfere with a downstream treatment process are at least partially removed via the flue gas (II).
  • the temperature within the rotary kiln (1) is monitored in the embodiment by means of a thermocouple and an infrared camera (5).
  • the camera is located at a distance outside of the rotary kiln at the rear of the outlet side on a wall of a downstream secondary combustion chamber (7).
  • the organic components are removed from the scrap. This is done by evaporating or splitting the organic constituents at the temperatures prevailing there, converting them into gaseous intermediates and incinerating them. These combustion products are fed together with any resulting metal vapors, compounds and dusts as flue gas (II) of the afterburner (7).
  • a controlled supply of oxygen in the form of air can be provided, with which the combustion is maintained. This is permitted to the extent that the temperature of the metal-containing waste (17) in the rotary tube is in the range between 750 ° C to 850 ° C.
  • the afterburning chamber (7) supplied flue gas (II) is first treated thermally at temperatures above 1000 ° C, so that the organic components therein are completely oxidized.
  • the residence time of the flue gas in the hot zone of the afterburning chamber is sufficiently large and is between 2 and 7 seconds.
  • the burnt flue gases separate out dusts when flowing through the downstream steam boiler (8). In the application example, these are collected in a dust chamber (9).
  • the thus treated flue gas (II) is fed to a steam boiler (8), in which it is cooled down to temperatures of 300 ° C to 350 ° C.
  • the steam boiler (8) is operated with water under a corresponding overpressure.
  • the cooled flue gases are then fed to a wet flue gas cleaning, where it is cooled, first by injecting water at 70 to 80 ° C in a quencher (10).
  • the flue gas (II) is first fed to an acidic rotary scrubber (12), in which an acidic scrubbing liquid is applied to spinner wheels, which produce a fine mist of liquid. As it flows through this mist, the flue gas (II) comes into close contact with the scrubbing liquid, so that further acid flue gas components and also fine dust are washed out and separated.
  • alkaline washing liquid in the exemplary embodiment mixed with sodium hydroxide added to remove residual acidic flue gas ingredients.
  • the few remaining in the flue gas (II) solid or liquid suspended matter are deposited in an electrostatically operated condensation filter (14).
  • the flue gas (II) treated in this way is subsequently fed to a catalytic secondary purification (15) and then discharged as purified exhaust air via the chimney (16).
  • the discharged metal conglomerates are in Fig. 3 to recognize.

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Description

Die Erfindung betrifft ein Verfahren zur Rückgewinnung von Metallen, insbesondere Edelmetallen aus Abfällen und/oder Materialien, wobei den Abfällen und/oder Materialien in einem bevorzugt kontinuierlichen Prozess durch thermische Behandlung in einer Prozesskammer die organischen Komponenten entzogen und oxidiert werden, sowie eine Anlage zur Durchführung des Verfahrens.The invention relates to a method for the recovery of metals, in particular precious metals from waste and / or materials, wherein the waste and / or materials in a preferably continuous process by thermal treatment in a process chamber, the organic components are removed and oxidized, and a plant for implementation of the procedure.

Im Stand der Technik sind Verfahren zur mechanischen Trennung der Komponenten bekannt, bei denen maximal bis zu 90 % der enthaltenen Wertmetalle zurückgewonnen werden können. Zusätzlich zur mechanischen Trennung ist eine Entsorgung der schadstoffbelasteten verbleibenden organischen Bestandteile notwendig.In the prior art, methods for mechanical separation of the components are known in which a maximum of up to 90% of the contained precious metals can be recovered. In addition to the mechanical separation, it is necessary to dispose of the contaminated remaining organic constituents.

Aus DE A 9420410 , DE A 9320018 und DE A 3518725 C2 ist ein Verfahren zur thermischen Behandlung von Elektronikschrotten durch Pyrolyse bekannt. Bei diesen Verfahren wird der im Rückstand verbleibende Pyrolysekoks im Rahmen einer weiteren Aufbereitung entfernt. In diesem Pyrolysekoks ist zum Teil mit hohen Konzentrationen an Dioxinen und Furanen zu rechnen. DE A 9420410 , DE A 9320018 und DE A 3518725 C2 befassen sich mit einem Verfahren zum thermischen Recycling von mit organischen Stoffen vermischten bzw. beschichteten oder ähnlich verunreinigten metallischen Gegenständen, wie zum Beispiel Farb- oder Öldosen bzw. -kanister, - fässer oder anderen Gebinden. Diese als Schrott zu bezeichnenden Ausgangskomponenten werden in eine Schwelkammer eingebracht, in der sie im Wesentlichen ohne Sauerstoffzufuhr zunächst thermisch behandelt werden. Diese Schwelkammer wird während der Schwelphase mit einer Temperatur im Bereich von ca. 250 bis 500°C, von außen beheizt betrieben und besitzt eine sich drehende Trommel, die während des Verfahrens mit einer Drehgeschwindigkeit von 1 bis 2 Umdrehung pro Minute betrieben wird. Während der Schwelphase entstehen brennbare Pyrolysegase oder brennbare Pyrolyseöle, die dazu verwendet werden können, die Schwelkammer auf Temperatur zu bringen. Dem Schwelprozess wird ein Oxidationsprozess nachgeschaltet, in welchem in derselben Kammer jedoch zeitlich nachfolgend durch Einbringen von Sauerstoff die während des Schwelprozesses erzeugten Pyrolysegase verbrannt werden. Letzteres kann auch in einer der Schwelkammer nachgeschalteten Nachbrennkammer erfolgen. Diese Schrift befasst sich auch mit dem Recyceln von Edelmetallstaub enthaltendem Kehricht wie er unter anderem in der Schmuckindustrie entstehen kann.Out DE A 9420410 . DE-A 9320018 and DE A 3518725 C2 is a method for thermal treatment of electronic scrap by pyrolysis known. In these processes, the pyrolysis coke remaining in the residue is removed as part of a further treatment. Partly high concentrations of dioxins and furans are expected in this pyrolysis coke. DE A 9420410 . DE-A 9320018 and DE A 3518725 C2 are concerned with a process for the thermal recycling of metallic objects mixed or coated with organic substances or similarly contaminated, such as paint or oil cans or cans, barrels or other containers. These starting components to be designated as scrap are introduced into a smoldering chamber in which they are first of all thermally treated without supplying oxygen. This carbonization chamber is operated during the carbonization phase at a temperature in the range of about 250 to 500 ° C, heated from the outside and has a rotating drum, which is operated during the process at a rotational speed of 1 to 2 revolutions per minute. During the smoldering phase, flammable pyrolysis gases or combustible pyrolysis oils are produced, which can be used to bring the smoldering chamber up to temperature. The smoldering process is followed by an oxidation process in which, in the same chamber, however, the pyrolysis gases generated during the smoldering process are subsequently burnt in by the introduction of oxygen. The latter can also be done in a Nachbrennkammer downstream of the smoldering chamber. This document is also concerned with the recycling of precious metal dust containing rubbish as it may arise, inter alia, in the jewelry industry.

Das Schwel-/Oxidationsverfahren wird in einer Veröffentlichung WLB Wasser, Luft und Boden 3/2000, auf der Seite 46 "Edelmetall-Recycling: Verschwelung statt Verbrennung" detailreicher beschrieben.The smoldering / oxidation process is described in more detail in a publication WLB Wasser, Luft und Boden 3/2000, on page 46 "Precious metal recycling: smoldering instead of combustion".

Alle diese Verfahren haben den Nachteil, dass mehr als 10 % des Metalls aus dem Schrott nicht wieder verwertbar ist und es sich um nacheinander ablaufende Prozesse handelt.All of these methods have the disadvantage that more than 10% of the metal from the scrap is not recyclable and it is about sequential processes.

Der Erfindung liegt daher die Aufgabe zugrunde, ein einfaches Verfahren bereitzustellen, mit dem aus metallhaltigen Ausgangsstoffen, insbesondere Elektronikschrott, ein Sekundärrohstoff in hohen Ausbeuten (>90 %) erreicht wird.The invention is therefore based on the object to provide a simple method with which from metal-containing starting materials, in particular electronic waste, a secondary raw material in high yields (> 90%) is achieved.

Gelöst wird die Aufgabe durch die in den Ansprüchen angegebene Erfindung, wobei jeder Anspruch eine eigenständige Lösung der oben genannten Aufgabe ist und jeder Anspruch mit jedem anderen Anspruch kombinierbar ist.The object is achieved by the invention specified in the claims, wherein each claim is an independent solution of the above object and each claim can be combined with any other claim.

Gegenstand der Erfindung ist ein Verfahren zur Rückgewinnung von Metallen aus metallhaltigen Abfällen und Materialien, dadurch gekennzeichnet, dass der metallhaltige Abfall vorzugsweise kontinuierlich in eine Prozesskammer eingeführt wird, unter kontinuierlicher intensiver Durchmischung thermisch behandelt wird, die organischen Komponenten kontinuierlich entzogen und anschließend oxidiert werden und die metallhaltigen Komponenten, bevorzugt als Metallkonglomerate und die weiteren anorganischen nichtmetallhaltigen Komponenten, im Wesentlichen kontinuierlich aus der Prozesskammer ausgetragen werden.The invention relates to a method for the recovery of metals from metal-containing wastes and materials, characterized in that the metal-containing waste is preferably introduced continuously into a process chamber, is thermally treated under continuous intensive mixing, the organic components are continuously removed and then oxidized and the metal-containing components, preferably as metal conglomerates and the other inorganic non-metal-containing components, are discharged substantially continuously from the process chamber.

Metallhaltige Abfälle und Materialien im Sinne der Erfindung sind üblicherweise Mischungen von Metallen inkl. Edelmetallen und organischen bzw. anorganischen Stoffen. Geeignet ist das Verfahren beispielsweise für Elektronikschrott und dient insbesondere der Vorbereitung für die Rückgewinnung von Metallen wie z.B. Kupfer, Zink, Zinn, Blei und insbesondere der Vorbereitung für die Rückgewinnung von Edelmetallen wie z.B. Gold, Silber, Platin und Palladium. Beispiele für zu behandelndes Material sind mit elektronischen Bauteilen bestückte Platinen oder Geräteteile oder komplette elektronische Geräte. Organische Bestandteile sind z. B. Kunststoffe, inkl. schwer entflammbares und/oder Brom-, Chlor-, oder andere Halogene enthaltendes Material eventuell mit nicht-metallischen Bestandteilen wie Glasfasern gemischt. Diese Abfälle werden bevorzugt in vorzerkleinerter Form in die Prozesskammer beschickt.Metal-containing wastes and materials in the context of the invention are usually mixtures of metals including precious metals and organic or inorganic substances. For example, the method is suitable for electronic scrap and is particularly useful for preparing for the recovery of metals such as metals. Copper, zinc, tin, lead and in particular the preparation for the recovery of precious metals, e.g. Gold, silver, platinum and palladium. Examples of material to be treated are printed circuit boards equipped with electronic components or parts of devices or complete electronic devices. Organic ingredients are z. As plastics, incl. Flame retardant and / or bromine, chlorine, or other halogen-containing material may be mixed with non-metallic constituents such as glass fibers. These wastes are preferably fed into the process chamber in pre-shredded form.

Anders als beim eingangs genannten Stand der Technik erfolgt der Prozess nicht in zeitlich hintereinander abfolgenden, gegebenenfalls durch Wartepausen voneinander getrennten Prozessschritten im Chargenbetrieb in einer vor dem Prozess zu beschickenden und nach dem Prozess wieder zu entleerenden Prozesskammer, sondern im Durchlaufverfahren. Der metallhaltige Abfall wird kontinuierlich dem Prozess zugeführt und in der Prozesskammer intensiv durchmischt.Unlike the prior art mentioned at the outset, the process does not take place in consecutive process steps, possibly separated from one another by waiting pauses, in batch operation in a process chamber to be charged before the process and to be emptied again after the process, but in a continuous process. The metal-containing waste is continuously fed to the process and thoroughly mixed in the process chamber.

US-A-3 817 697 offenbart ein reduktives Verfahren (Pyrolyse) zur Entölung von Metallspänen bei dem zur Temperaturkontrolle kein Kühlmittel in die Prozesskammer dazugegeben wird. US-A-3,817,697 discloses a reductive process (pyrolysis) for de-oiling metal shavings in which no coolant is added to the process chamber for temperature control.

US-A-4 415 360 beschreibt ein reduktives Verfahren zur Rückgewinnung von Metallen aus Abfällen wie Elektronikschrott durch thermische Behandlung in einem Kaldo-Verbrenner, wobei optional auch Sauerstoff in substöchiometrischen Verhältnissen und/oder Öl zugeführt werden kann (S. 5 Zeile 35 bis 49). US-A-4,415,360 describes a reductive process for recovering metals from wastes such as electronic scrap by thermal treatment in a Kaldo combustor, optionally also oxygen in substoichiometric ratios and / or oil can be supplied (page 5 lines 35 to 49).

US2005/0077658A1 betrifft ein System zur Behandlung von Dämpfen aus Metallrückgewinnungsöfen. US2005/0077658A1 bezieht sich nicht auf den Einsatz von thermischen Verfahren auf metallhaltige Abfälle selber, sondern beschreibt erst die Behandlung von Dämpfen die aus der thermischen Behandlung der metallhaltigen Abfälle entstanden sind. US2005 / 0077658A1 relates to a system for treating vapors from metal recovery furnaces. US2005 / 0077658A1 does not refer to the use of thermal processes on metal-containing waste itself, but first describes the treatment of vapors arising from the thermal treatment of metal-containing waste.

Pankratz, E.: "Aufarbeitung von verbrauchten Ni-Fettkatalysatoren" FAT SCI. TECHNOL., Bd. 95, Juli 1993 (1993-07), Seiten 487-490 und Pankratz, E.: "Umweltschonende Aufarbeitung von Ni-haltigen Katalysatoren" FAT SCI. TECHNOL., Bd. 97, Juni 1995 (1995-06), Seiten 508-512 ) betreffen ein Verfahren zur Rückgewinnung von Ni-haltigen Abfällen (Fettkatalysatoren) durch oxidative Verbrennung in einem Drehrohrofen. Pankratz, E .: "Processing of spent Ni-fat catalysts" FAT SCI. TECHNOL., Vol. 95, July 1993 (1993-07), pages 487-490 and Pankratz, E .: "Environmentally friendly processing of Ni-containing catalysts" FAT SCI. TECHNOL., Vol. 97, June 1995 (1995-06), pages 508-512 ) relate to a process for the recovery of Ni-containing wastes (fatty catalysts) by oxidative combustion in a rotary kiln.

US-A-5 013 533 betrifft ein Verfahren zur Rückgewinnung von Metallen aus verbrauchten Katalysatoren. Auch in diesem Verfahren wird ein Drehrohrofen (22) eingesetzt in den Luft (18) eingeströmt werden kann. Die oxidative Verbrennung findet bei Temperaturen von 177°C bis 870°C statt. Alle diese Verfahren haben den Nachteil, dass mehr als 10 % des Metalls aus dem Schrott nicht wieder verwertbar ist und es sich um nacheinander ablaufende Prozesse handelt. US-A-5 013 533 relates to a process for the recovery of metals from spent catalysts. Also in this method, a rotary kiln (22) is used in the air (18) can be flowed. Oxidative combustion takes place at temperatures of 177 ° C to 870 ° C. All of these methods have the disadvantage that more than 10% of the metal from the scrap is not recyclable and it is about sequential processes.

Der Erfindung liegt daher die Aufgabe zugrunde, ein einfaches Verfahren bereitzustellen, mit dem aus metallhaltigen Ausgangsstoffen, insbesondere Elektronikschrott, ein Sekundärrohstoff in hohen Ausbeuten (>90 %) erreicht wird.The invention is therefore based on the object to provide a simple method with which from metal-containing starting materials, in particular electronic waste, a secondary raw material in high yields (> 90%) is achieved.

Gelöst wird die Aufgabe durch die in den Ansprüchen angegebene Erfindung, wobei jeder Anspruch eine eigenständige Lösung der oben genannten Aufgabe ist und jeder Anspruch mit jedem anderen Anspruch kombinierbar ist.The object is achieved by the invention specified in the claims, wherein each claim is an independent solution of the above object and each claim can be combined with any other claim.

Gegenstand der Erfindung ist ein Verfahren zur Rückgewinnung von Metallen aus metallhaltigen Abfällen und Materialien bei dem der metallhaltige Abfall vorzugsweise kontinuierlich in eine Prozesskammer eingeführt wird, unter kontinuierlicher intensiver Durchmischung thermisch behandelt wird und unter Zuleitung von sauerstoffhaltigen Gasen behandelt wird die flüchtig restlichen, organischen Komponenten kontinuierlich entzogen und anschließend oxidiert werden und die metallhaltigen Komponenten, bevorzugt als Metallkonglomerate und die weiteren anorganischen nichtmetallhaltigen Komponenten, im Wesentlichen kontinuierlich aus der Prozesskammer ausgetragen werden, dadurch gekennzeichnet, dass die Verbrennungstemperatur in der Prozesskammer mittels Temperaturerfassungsmittel, Temperaturregelungsmitteln und einer Temperatursteuerung mittels Zugabe von Kühlmittel in die Prozesskammer, in einem Bereich von 400 bis 1100°C gehalten wird.The invention relates to a method for the recovery of metals from metal-containing waste and materials in which the metal-containing waste is preferably introduced continuously into a process chamber, is thermally treated under continuous intensive mixing and treated under supply of oxygen-containing gases, the volatile residual organic components continuously removed and then oxidized and the metal-containing components, preferably as metal conglomerates and the others inorganic non-metal-containing components, are discharged substantially continuously from the process chamber, characterized in that the combustion temperature in the process chamber by means of temperature detection means, temperature control means and a temperature control means of adding coolant into the process chamber, in a range of 400 to 1100 ° C is maintained.

Metallhaltige Abfälle und Materialien im Sinne der Erfindung sind üblicherweise Mischungen von Metallen inkl. Edelmetallen und organischen bzw. anorganischen Stoffen. Geeignet ist das Verfahren beispielsweise für Elektronikschrott und dient insbesondere der Vorbereitung für die Rückgewinnung von Metallen wie z.B. Kupfer, Zink, Zinn, Blei und insbesondere der Vorbereitung für die Rückgewinnung von Edelmetallen wie z.B. Gold, Silber, Platin und Palladium. Beispiele für zu behandelndes Material sind mit elektronischen Bauteilen bestückte Platinen oder Geräteteile oder komplette elektronische Geräte. Organische Bestandteile sind z. B. Kunststoffe, inkl. schwer entflammbares und/oder Brom-, Chlor-, oder andere Halogene enthaltendes Material eventuell mit nicht-metallischen Bestandteilen wie Glasfasern gemischt. Diese Abfälle werden bevorzugt in vorzerkleinerter Form in die Prozesskammer beschickt.Metal-containing wastes and materials in the context of the invention are usually mixtures of metals including precious metals and organic or inorganic substances. For example, the method is suitable for electronic scrap and is particularly useful for preparing for the recovery of metals such as metals. Copper, zinc, tin, lead and in particular the preparation for the recovery of precious metals, e.g. Gold, silver, platinum and palladium. Examples of material to be treated are printed circuit boards equipped with electronic components or parts of devices or complete electronic devices. Organic ingredients are z. As plastics, incl. Flame retardant and / or bromine, chlorine, or other halogen-containing material may be mixed with non-metallic constituents such as glass fibers. These wastes are preferably fed into the process chamber in pre-shredded form.

Anders als beim eingangs genannten Stand der Technik erfolgt der Prozess nicht in zeitlich hintereinander abfolgenden, gegebenenfalls durch Wartepausen voneinander getrennten Prozessschritten im Chargenbetrieb in einer vor dem Prozess zu beschickenden und nach dem Prozess wieder zu entleerenden Prozesskammer, sondern im Durchlaufverfahren. Der metallhaltige Abfall wird kontinuierlich dem Prozess zugeführt und in der Prozesskammer intensiv durchmischt.Unlike the prior art mentioned at the outset, the process does not take place in consecutive process steps, possibly separated from one another by waiting pauses, in batch operation in a process chamber to be charged before the process and to be emptied again after the process, but in a continuous process. The metal-containing waste is continuously fed to the process and thoroughly mixed in the process chamber.

Intensive Durchmischung im Sinne der Erfindung bedeutet, dass der Abfall mittels eines Drehrohrs, einer Rostfeuerung oder in einem Wirbelschichtverfahren ständig in Bewegung gehalten wird oder in die Prozesskammer fein verteilt eingebracht wird.Intensive mixing in the sense of the invention means that the waste is constantly kept in motion by means of a rotary tube, a grate furnace or in a fluidized bed process, or is introduced finely distributed in the process chamber.

Mit thermischer Behandlung ist gemeint, dass in der Prozesskammer Temperaturen von 400 bis 1100°C, bevorzugt 600 bis 900°C, in einer weiteren bevorzugten Ausführungsform 500 bis 900°C, besonders bevorzugt 700 bis 850°C (Fig. 2b, Phase B), gehalten werden.By thermal treatment is meant that in the process chamber temperatures of 400 to 1100 ° C, preferably 600 to 900 ° C, in another preferred embodiment 500 to 900 ° C, particularly preferably 700 to 850 ° C ( Fig. 2b , Phase B).

Um den Prozess zu unterstützen, können der Prozesskammer Gase, z.B.sauerstoffhaltige Gase, gezielt zugeleitet werden.To aid the process, gases, such as oxygen-containing gases, may be selectively supplied to the process chamber.

Die Prozesskammer wird bevorzugt von einem Drehrohrofen ausgebildet, der im Wesentlichen aus einem langgestreckten Drehrohr besteht, welches einseitig eine Beschickungsöffnung ausbildet. Zufolge der Drehung des Drehrohres und der Neigung desselben wird der beschickungsseitig in das Drehrohr gegebene Schrott auf dem Boden des Rohres intensiv durchmischt und weitertransportiert. Das in der Prozesskammer insbesondere im Drehrohr liegende Material wird in einer sich der Aufheizzone A anschließenden Verbrennungszone B innerhalb eines vorgegebenen Temperaturbereiches thermisch behandelt (Fig. 2b). Beschickungsseitig kann auch eine Stützfeuerung vorgesehen sein, um die thermischen Prozesse einzuleiten bzw. zu unterstützen.The process chamber is preferably formed by a rotary kiln, which essentially consists of an elongated rotary tube, which forms a feed opening on one side. As a result of the rotation of the rotary tube and the inclination thereof, the scrap placed on the feed side into the rotary tube is intensively mixed on the bottom of the tube and transported further. The material lying in the process chamber, in particular in the rotary tube, is thermally treated in a combustion zone B adjoining the heating zone A within a predetermined temperature range ( Fig. 2b ). On the supply side can also be provided a support firing to initiate or support the thermal processes.

Vorzugsweise wird die Aufwärmung des Schrotts auf 700 bis 850°C durch eine Stützfeuerung (3), die sich auf der Beschickungsseite (1') des Drehrohrofens (1) befindet, eingeleitet.Preferably, the heating of the scrap to 700 to 850 ° C by a Stützfeuerung (3), which is located on the feed side (1 ') of the rotary kiln (1), initiated.

Die Prozesstemperatur wird mit geeigneten Temperaturerfassungsmitteln (wie z.B. Thermo-element, Infrarotkamera), Temperaturregelungsmitteln (wie z.B. elektronischer Bildauswertung von Infrarotkameradaten) und Temperatursteuerungsmitteln (wie z.B. Zugabe von Kühlmitteln in die Prozesskammer) in einem geeigneten Bereich gehalten.The process temperature is maintained within a suitable range with suitable temperature sensing means (such as a thermocouple, infrared camera), temperature control means (such as electronic image analysis of infrared camera data) and temperature control means (such as adding coolants to the process chamber).

Vorzugsweise ist die Infrarotkamera (5) der Austrittsseite (1") und insbesondere einer vom Ende des Drehrohrs beabstandeten Wandung einer Nachbrennkammer (7) zugeordnet.Preferably, the infrared camera (5) is associated with the outlet side (1 ") and in particular with a wall spaced from the end of the rotary tube of a secondary combustion chamber (7).

Bei solchen Temperaturen entweichen die organischen Komponenten in der Verbrennungszone; das nicht flüchtige Verbrennungsprodukt bleibt auf dem Boden der Prozesskammer bzw. des Drehrohres und wird der Austrittsseite zugeführt, wo es als Rückstand austritt, der im Wesentlichen nur noch Metallbestandteile und anorganische Nichtmetallbestandteile enthält, die einer anschließenden Verarbeitung (z. B. Verhüttung) zugeführt werden.At such temperatures, the organic components escape in the combustion zone; the non-volatile combustion product remains at the bottom of the process chamber or rotary tube and is fed to the exit side, where it emerges as a residue containing essentially only metal components and inorganic non-metal constituents, which are fed to a subsequent processing (eg smelting) ,

In einer bevorzugten Ausführungsform wird der metallhaltige Abfall von der Beschickungsseite (1') zur Austrittsseite (1") transportiert, wobei der Abfall. zunächst in einer Aufheizzone (A) gegebenenfalls mit Hilfe eines Stützfeuers (3) aufgeheizt wird, dann in einer sich daran anschließenden Verbrennungszone (B) die organischen Komponenten von den metallischen Komponenten thermisch getrennt und zumindest teilweise bevorzugt größtenteils verbrannt werden und schließlich die nicht flüchtigen Metallbestandteile zusammen mit gegebenenfalls vorhandenen nicht flüchtigen anorganischen Bestandteilen auf der der Beschickungsseite der Prozesskammer gegenüberliegenden Austrittsseite im Wesentlichen kontinuierlich austreten.In a preferred embodiment, the metal-containing waste is transported from the feed side (1 ') to the discharge side (1 "), the waste initially being heated in a heating zone (A). optionally with the aid of a support fire (3) is heated, then in an adjoining combustion zone (B), the organic components of the metallic components thermally separated and at least partially preferably mostly burned and finally the non-volatile metal components together with any non-volatile inorganic Constituents on the feed side of the process chamber opposite outlet side substantially continuously emerge.

Die thermisch abgetrennten organischen Komponenten werden als Rauchgas (II) abtransportiert, wobei eine nicht unerhebliche Menge der organischen Bestandteile innerhalb der Verbrennungszone oxidiert wird. Auch diese Verbrennungsprodukte sind im Rauchgas (II) enthalten. Innerhalb des Rauchgases (II) können sich darüber hinaus Metalldämpfe und sich gegebenenfalls in der Prozesskammer gebildete Metallverbindungen befinden. Die Prozessführung innerhalb der Prozesskammer ist vorzugsweise so gewählt (s. o.), dass der Anteil des Metalls, das als Gas- oder als Partikel in die Rauchgasreinigung gelangt, bei den zu verwertenden Metallen unter 7 %, bevorzugt unter 3 %, besonders bevorzugt unter 1 % liegt. Metalle wie z. B. Al, Mg, Sb, As, die ein nachgeschaltetes Aufbereitungsverfahren stören können, können zumindest teilweise über das Rauchgas (II) abgeführt werden.The thermally separated organic components are transported away as flue gas (II), whereby a not inconsiderable amount of the organic constituents within the combustion zone is oxidized. These combustion products are contained in the flue gas (II). Within the flue gas (II) may also be metal vapors and possibly formed in the process chamber metal compounds. The process management within the process chamber is preferably selected (see above) such that the proportion of the metal entering the flue gas purification as gas or as particles is below 7%, preferably below 3%, particularly preferably below 1%, of the metals to be utilized. lies. Metals such as B. Al, Mg, Sb, As, which can interfere with a downstream treatment process can be removed at least partially via the flue gas (II).

In einer bevorzugten Ausführungsform beträgt die Aufenthaltszeit des Rauchgases in der heißen Zone der Nachbrennkammer zwischen 2 und 7 Sekunden. Die ausgebrannten Rauchgase scheiden beim Durchströmen des nachgeschalteten Dampfkessels (8) Stäube ab. Diese in einer Staubkammer (9) gesammelt.In a preferred embodiment, the residence time of the flue gas in the hot zone of the afterburner is between 2 and 7 seconds. The burnt flue gases separate out dusts when flowing through the downstream steam boiler (8). These collected in a dust chamber (9).

Die die Prozesskammer flüchtig verlassenden Komponenten bestehen insbesondere aus Rauchgasen der bereits erfolgten Verbrennung, unvollständig oxidierten organischen Verbindungen, Metalldämpfen, -Verbindungen, Stäuben und anderen anorganischen Verbindungen. Diese werden einer der Prozesskammer nachgeordneten Nachbrennkammer zugeführt, in welcher die vollständige Oxidation aller noch enthaltenen restlichen organischen Verbindungen erfolgt. Hierzu ist auch die Verweilzeit des Rauchgases (II) in der Nachbrennkammer mit bevorzugt > 2 s ausreichend groß. Die Temperatur innerhalb der Nachbrennkammer ist ausreichend hoch und liegt insbesondere über 850°C, bevorzugt über 1000°C, in einer weiteren Ausführungsform insbesondere über 800°C, bevorzugt über 900°C. Bei solchen Temperaturen werden Dioxine und Furane vollständig zerstört. Das mit anorganischen Schadstoffen beladene Rauchgas (II) wird anschließend zur Einhaltung niedriger Emissionswerte mehrstufig gereinigt. Zuvor kann dem Rauchgas (II) durch Abkühlen Wärmeenergie entzogen werden, die in geeigneter Form anderweitig genutzt werden kann. Bevorzugt wird die anschließende Rauchgasreinigung wie folgt durchgeführt: Das Rauchgas (II) wird im ersten Schritt in einer sogenannten Quenche (10) auf eine Temperatur unter 100°C, bevorzugt auf ca. 70 bis 80°C, vorzugsweise durch Einspritzen von Wasser, abgekühlt. Der Quenche schließen sich Wäscher an, um weitere Bestandteile aus dem Rauchgas (II) zu entfernen. Hierbei handelt es sich um Rotationswäscher, die sauer und/oder alkalisch betrieben werden. Anschließend erfolgt eine Entfernung des Feinstaubes in einem Kondensationselektrofilter (14). Im letzten Schritt wird die Konzentration an ggf. im Rauchgas vorhandenen Dioxinen und Furanen sowie Stickoxiden an einem Katalysator deutlich reduziert. Die im Abwasser der Rauchgasreinigung enthaltenen restlichen Wertmetallanteile können über eine nachgeschaltete Abwasserbehandlungsanlage einer Verwertung zugeführt, werden.The components leaving the process chamber consist in particular of flue gases of combustion already carried out, incompletely oxidized organic compounds, metal vapors, compounds, dusts and other inorganic compounds. These are fed to a subsequent combustion chamber of the process chamber, in which the complete oxidation of all residual organic compounds still contained. For this purpose, the residence time of the flue gas (II) in the secondary combustion chamber with preferably> 2 s is sufficiently large. The temperature within the afterburning chamber is sufficiently high and is in particular above 850 ° C., preferably above 1000 ° C., in a further embodiment in particular above 800 ° C., preferably above 900 ° C. At such temperatures, dioxins and furans are completely destroyed. The laden with inorganic pollutants flue gas (II) is then cleaned in several stages to maintain low emissions. Previously, the flue gas (II) can be removed by cooling heat energy, which can be used in a suitable form elsewhere. Preferably, the subsequent flue gas cleaning is carried out as follows: The flue gas (II) is in the first step in a so-called quenches (10) on a Temperature below 100 ° C, preferably to about 70 to 80 ° C, preferably by injection of water, cooled. The quencher is followed by scrubbers to remove further components from the flue gas (II). These are rotary scrubbers that are operated acid and / or alkaline. Subsequently, the fine dust is removed in a condensation electric filter (14). In the last step, the concentration of possibly present in the flue gas dioxins and furans and nitrogen oxides on a catalyst is significantly reduced. The remaining value metal fractions contained in the waste water of the flue gas cleaning can be recycled via a downstream wastewater treatment plant.

Die gereinigte Abluft wird vorzugsweise über einen Kamin (16) abgegeben.The cleaned exhaust air is preferably discharged through a chimney (16).

Als Katalysatoren können alle dem Fachmann für die katalytische Nachreinigung bekannten Substanzen benutzt werden.As catalysts, it is possible to use all substances known to the person skilled in the art for catalytic secondary purification.

Bevorzugt wird der Prozess so gerührt, dass es im Rahmen der thermischen Behandlung zu einem Aufschmelzen einzelner niedrigschmelzender Metallanteile kommt, die wiederum höherschmelzende Metalle lösen. Diese Metalllösung nimmt insbesondere auch Edelmetallbestandteile mit auf. Diese Metallanteile finden sich in Form von Metallkonglomeraten in dem ausgetragenen Rückstand wieder. Die Metallkonglomerate können abgetrennt werden. Die Bildung dieser Metallkonglomerate kann durch eine entsprechende Konzentration von Eisen und/oder Loten (z.B. Zinn, Blei, Wismut) gesteigert werden. Hierzu können Eisen, Lote und/oder Flussmittel auch zugegeben werden.Preferably, the process is stirred so that it comes in the context of thermal treatment to melting individual low-melting metal components, which in turn solve higher melting metals. In particular, this metal solution also includes precious metal components. These metal components are found again in the form of metal conglomerates in the discharged residue. The metal conglomerates can be separated. The formation of these metal conglomerates can be enhanced by a corresponding concentration of iron and / or solders (e.g., tin, lead, bismuth). For this purpose, iron, solders and / or flux can also be added.

Der Vorteil der Erfindung liegt darin, dass die Metallkonglomerate einfach von den festen anorganischen Bestandteile abgetrennt werden können und in einem nachgeschalteten Aufbereitungsverfahren (z. B. Verhüttung) direkt in einen sehr späten Teilschritt des Verhüttungsprozesses eingetragen werden können. Hierdurch kann die Effizienz der Metallrückgewinnung im nachgeschalteten Aufbereitungsverfahren gesteigert werden.The advantage of the invention is that the metal conglomerates can be easily separated from the solid inorganic constituents and can be added directly to a very late step of the smelting process in a subsequent treatment process (eg smelting). This can increase the efficiency of metal recovery in the downstream treatment process.

Ein weiterer Gegenstand der Erfindung ist eine Anlage zur thermischen Behandlung metallhaltiger Abfälle und Materialien, beinhaltend einen Drehrohrofen (1), eine kontinuierlich arbeitende Beschickungsvorrichtung (6), eine Kühlmittelzugabelanze (4) die von der Beschickungsseite (1') her in den Drehofen (1) hineinragt, mindestens eine Nachbrennkammer, mindestens einen Abhitzekessel, mindestens eine Quenche, ein Rotationswäscher oder mindestens zwei hintereinandergeschaltete Rotationswäscher, mindestens ein Kondensationselektrofilterund mindestens eine katalytische Nachreinigung für die Rauchgase.Another object of the invention is a plant for the thermal treatment of metal-containing wastes and materials, comprising a rotary kiln (1), a continuously operating charging device (6), a Kühlmittelzugabelanze (4) from the feed side (1 ') forth in the rotary kiln (1 ), at least one afterburner chamber, at least one waste heat boiler, at least one quencher, a rotary scrubber or at least two successive rotary scrubbers, at least one condensation electrostatic precipitator and at least one post catalytic purification for the flue gases.

Der Drehrohrofen (1) besteht aus einem länglichen Rohr, das für industrielle Anwendungen vorzugsweise 10 bis 13 m lang ist, wobei auch andere gängige Längen verwirklicht werden können. Dieses Rohr ist vorzugsweise gegenüber der Horizontalen geneigt und mit einem feuerfesten Material ausgemauert.The rotary kiln (1) consists of an elongated tube, which is preferably 10 to 13 m long for industrial applications, whereby other common lengths are realized can. This tube is preferably inclined relative to the horizontal and lined with a refractory material.

Zur Abkühlung ist eine Kühlmittelzugabelanze (4) eingebaut, die von der Beschickungsseite (1') her in den Drehrohrofen (1) hineinragt und aus deren Düse (4') Wasser ein Kühlmittel in den Ofen gebracht wird.For cooling, a Kühlmittelzugabelanze (4) is installed, which protrudes from the feed side (1 ') forth in the rotary kiln (1) and from the nozzle (4') water, a coolant is placed in the oven.

In einer weiteren Ausführungsform wird die Temperatur innerhalb des Drehrohrofens (1) mit einem Thermoelement und einer Infrarotkamera (5) überwacht.In a further embodiment, the temperature within the rotary kiln (1) is monitored with a thermocouple and an infrared camera (5).

Bevorzugt werden innerhalb der Verbrennungszone (B) dem Schrott die organischen Bestandteile entzogen und die Verbrennungsprodukte zusammen mit gegebenenfalls entstehenden Metalldämpfen, Metallverbindungen und Stäuben als Rauchgas (II) der Nachbrennkammer (7) zugeleitet.Within the combustion zone (B), the organic constituents are preferably removed from the scrap and the combustion products, together with any metal vapors, metal compounds and dusts which may be formed, are fed as flue gas (II) to the afterburner chamber (7).

Ebenfalls bevorzugt ist eine kontrollierte Sauerstoffzufuhr zur Aufrechterhaltung der Verbrennung.Also preferred is a controlled oxygen supply to maintain combustion.

Ausführungsbeispiel:Embodiment:

Ein Ausführungsbeispiel der Erfindung wird nachfolgend anhand beigefügter Figuren erläutert, ohne dabei auf diese beschränkt zu sein.An embodiment of the invention will be explained below with reference to attached figures, without being limited to these.

Dabei werden folgende Bezugzeichen verwendet:

1
Drehrohrofen
1'
Beschickungsseite
1"
Austrittseite
2
Wasserbad
3
Stützfeuerung
4
Kühlmittelzugabelanze
4'
Düse
5
Thermoelement mit Infrarotkamera
6
Beschickvorrichtung
7
Nachbrennkammer
8
Dampfkessel
9
Staubkammer
10
Quenche
11
Auslass der wasserlöslichen Stoffe und Stäube
12
Sauerer Rotationswäscher
13
Alkalischer Rotationswäscher
14
Kondensationselektrofilter
15
Katalytische Nachreinigungskammer
16
Kamin
17
Metallhaltiger Abfall
18
Flamme
19
Konglomerate
I
Fester Rückstand
II
Rauchgas
A
Aufheizphase
B
Verbrennungszone
C
Bildung der Metallkonglomerate
The following references are used:
1
Rotary kiln
1'
loading side
1"
exit side
2
water bath
3
auxiliary firing
4
Coolant addition lance
4 '
jet
5
Thermocouple with infrared camera
6
charging device
7
afterburner chamber
8th
steam boiler
9
dust chamber
10
quench
11
Outlet of water-soluble substances and dusts
12
Acid rotary scrubber
13
Alkaline rotary scrubber
14
Condensation electrostatic precipitator
15
Catalytic post-purification chamber
16
fireplace
17
Metal-containing waste
18
flame
19
conglomerates
I
Fixed residue
II
flue gas
A
heating phase
B
combustion zone
C
Formation of metal conglomerates

Es zeigen:

Fig. 1
den schematischen Aufbau einer Vorrichtung zur Durchführung des Verfahrens;
Fig. 2a
die vergrößerte Darstellung der von einem Drehrohr gebildeten Prozesskammer und
Fig. 2b
schematisch den Temperaturverlauf durch das Drehrohr gemäß Fig. 2a.
Fig. 3
ein Foto von einem ausgetragenen (Metall-)Konglomerat.
Show it:
Fig. 1
the schematic structure of an apparatus for performing the method;
Fig. 2a
the enlarged view of the process chamber formed by a rotary tube and
Fig. 2b
schematically the temperature profile through the rotary tube according to Fig. 2a ,
Fig. 3
a photograph of a discharged (metal) conglomerate.

Die Vorrichtung zur Durchführung des Verfahrens besteht im Wesentlichen aus einem Drehrohrofen (1), das aus einem länglichen Rohr von ca. 10 bis 13 m besteht. Dieses Rohr ist gegenüber der Horizontalen geneigt und mit einem feuerfesten Material ausgemauert. Die Neigung und das Drehen des Rohres mit 10 bis 20 Umdrehungen pro Stunde [Uph] um seine Längsachse bewirken, dass der sich auf der Beschickungsseite 1' über eine Beschickungsvorrichtung (6) in das Drehrohr kontinuierlich eingetragene metallhaltige Abfall durch das Rohr hin zu der der Beschickungsseite (1') gegenüberliegenden Austrittsseite (1") bewegt. Dabei wird der zu behandelnde metallhaltige Abfall (17) im Drehrohr (1) ständig in Bewegung gehalten und intensiv durchmischt.The apparatus for carrying out the method consists essentially of a rotary kiln (1), which consists of an elongated tube of about 10 to 13 m. This tube is inclined relative to the horizontal and lined with a refractory material. The inclination and rotation of the tube at 10 to 20 revolutions per hour [Uph] about its longitudinal axis cause the metal-containing waste continuously introduced on the feed side 1 'via a feed device (6) into the rotary tube to pass through the tube In this case, the metal-containing waste (17) to be treated is kept constantly in motion in the rotary tube (1) and intensively mixed.

Auf der Beschickungsseite (1') wird das Drehrohr mit dem zu behandelnden Elektronikschrott beschickt. Dieser durchläuft das Drehrohr in einer Zeit von ca. 1,5 Stunden. Größere Teile des Elektronikschrotts, wie z. B. Chassis, welche aus Metall, insbesondere Eisen und aus Kunststoffen bestehen, können zerkleinert und insbesondere geschreddert sein.On the feed side (1 '), the rotary tube is charged with the electronic waste to be treated. This passes through the rotary tube in a time of about 1.5 hours. Larger parts of the electronic waste, such. As chassis, which consist of metal, especially iron and plastic, can be crushed and shredded in particular.

Dieser Schrott durchwandert aufgrund der Drehung des Drehrohres zunächst die mit A bezeichnete Aufheizphase innerhalb des Drehrohrofens (1). Mit Hilfe einer Stützfeuerung (3), die sich auf der Beschickungsseite (1') des Drehrohrofens (1) befindet, wird die zur Aufwärmung des Schrottes erforderliche Wärme in den Drehrohrofen eingeleitet, dies erfolgt beispielsweise mit der langgestreckten und mit der Bezugsziffer (18) bezeichneten Flamme. Je nach Heizwert des Schrottes kann eine Abkühlung erforderlich sein, um die Verbrennungstemperatur im besonders bevorzugten Bereich zwischen 700 bis 850°C zu halten. Dieser Temperaturbereich soll in der mit B bezeichneten Verbrennungszone gehalten werden. Zur gegebenenfalls erforderlichen Abkühlung ist eine Kühlmittelzugabelanze (4) vorgesehen, die im Ausführungsbeispiel von der Beschickungsseite (1') her in das Drehrohrofen (1) hineinragt und aus deren Düse (4') Wasser oder ein ähnlich geeignetes Kühlmittel in den Ofen gebracht wird.Due to the rotation of the rotary tube, this scrap first passes through the heating phase designated A within the rotary kiln (1). By means of a Stützfeuerung (3), which is located on the feed side (1 ') of the rotary kiln (1), the heat required for the heating of the scrap heat is introduced into the rotary kiln, this is done for example with the elongated and the reference numeral (18). designated flame. Depending on the calorific value of the scrap, cooling may be required to maintain the combustion temperature in the most preferred range between 700 to 850 ° C. This temperature range should be kept in the combustion zone designated B. For optionally required cooling a Kühlmittelzugabelanze (4) is provided which projects in the embodiment of the feed side (1 ') forth in the rotary kiln (1) and from the nozzle (4') water or a similar suitable coolant is placed in the oven.

Der sich auf dem Boden des Drehrohres von der Beschickungsseite (1') bis zur Austrittsseite (1") bewegende zu behandelnde metallhaltige Abfall (17) wird somit in dem gewünschten Temperaturbereich gehalten, in welchem die Oxidation der organischen Bestandteile im metallhaltigen Abfall möglichst vollständig erzielt wird. Gleichzeitig soll die Temperatur aber nicht zu hoch werden, um zu vermeiden, dass nennenswerte Mengen der rückzugewinnenden metallischen Komponenten über das Rauchgas (II) abtransportiert werden. Metalle wie z. B. Al, Mg, Sb, As, die ein nachgeschaltetes Aufbereitungsverfahren stören können, werden zumindest teilweise über das Rauchgas (II) abgeführt.The metal-containing waste (17) to be treated which moves on the bottom of the rotary tube from the feed side (1 ') to the outlet side (1 ") thus becomes the desired one Temperature range maintained in which the oxidation of the organic components in the metal-containing waste is achieved as completely as possible. At the same time, however, the temperature should not become too high in order to avoid that significant quantities of the metallic components to be recovered are removed via the flue gas (II). Metals such as B. Al, Mg, Sb, As, which can interfere with a downstream treatment process are at least partially removed via the flue gas (II).

Die Temperatur innerhalb des Drehrohrofens (1) wird im Ausführungsbeispiel mittels Thermoelement und einer Infrarotkamera (5) überwacht. Die Kamera befindet sich in einer Entfernung außerhalb des Drehrohrofens rückwärtig der Austrittsseite an einer Wandung einer nachgeordneten Nachbrennkammer (7).The temperature within the rotary kiln (1) is monitored in the embodiment by means of a thermocouple and an infrared camera (5). The camera is located at a distance outside of the rotary kiln at the rear of the outlet side on a wall of a downstream secondary combustion chamber (7).

Innerhalb der Verbrennungszone (B) werden dem Schrott die organischen Bestandteile entzogen. Dies erfolgt dadurch, dass die organischen Bestandteile bei den dort herrschenden Temperaturen abdampfen bzw. aufgespalten werden, sich in gasförmige Zwischenprodukte umwandeln und verbrannt werden. Diese Verbrennungsprodukte werden zusammen mit gegebenenfalls entstehenden Metalldämpfen, -verbindungen und Stäuben als Rauchgas (II) der Nachbrennkammer (7) zugeleitet.Within the combustion zone (B), the organic components are removed from the scrap. This is done by evaporating or splitting the organic constituents at the temperatures prevailing there, converting them into gaseous intermediates and incinerating them. These combustion products are fed together with any resulting metal vapors, compounds and dusts as flue gas (II) of the afterburner (7).

Bevorzugt kann eine kontrollierte Sauerstoffzufuhr in Form von Luft vorgesehen sein, mit der die Verbrennung aufrecht erhalten wird. Dies wird in dem Umfang zugelassen, dass sich die Temperatur des im Drehrohr befindlichen metallhaltigen Abfalls (17) im Bereich zwischen 750°C bis 850°C bewegt.Preferably, a controlled supply of oxygen in the form of air can be provided, with which the combustion is maintained. This is permitted to the extent that the temperature of the metal-containing waste (17) in the rotary tube is in the range between 750 ° C to 850 ° C.

Das der Nachbrennkammer (7) zugeführte Rauchgas (II) wird zunächst thermisch bei Temperaturen über 1000°C behandelt, so dass die darin befindlichen organischen Komponenten komplett oxidiert werden. Die Aufenthaltszeit des Rauchgases in der heißen Zone der Nachbrennkammer ist ausreichend groß und beträgt zwischen 2 und 7 Sekunden. Die ausgebrannten Rauchgase scheiden beim Durchströmen des nachgeschalteten Dampfkessels (8) Stäube ab. Im Anwendungsbeispiel werden diese in einer Staubkammer (9) gesammelt.The afterburning chamber (7) supplied flue gas (II) is first treated thermally at temperatures above 1000 ° C, so that the organic components therein are completely oxidized. The residence time of the flue gas in the hot zone of the afterburning chamber is sufficiently large and is between 2 and 7 seconds. The burnt flue gases separate out dusts when flowing through the downstream steam boiler (8). In the application example, these are collected in a dust chamber (9).

Zur Nutzung der Wärmeenergie wird das so behandelte Rauchgas (II) einem Dampfkessel (8) zugeleitet, in welchem es auf Temperaturen von 300°C bis 350°C heruntergekühlt wird. Der Dampfkessel (8) wird mit Wasser unter entsprechendem Überdruck betrieben.To use the heat energy, the thus treated flue gas (II) is fed to a steam boiler (8), in which it is cooled down to temperatures of 300 ° C to 350 ° C. The steam boiler (8) is operated with water under a corresponding overpressure.

Die abgekühlten Rauchgase werden anschließend einer nassen Rauchgasreinigung zugeführt, dort wird es, zunächst durch Einspritzen von Wasser auf 70 bis 80°C in einer Quenche (10) abgekühlt.The cooled flue gases are then fed to a wet flue gas cleaning, where it is cooled, first by injecting water at 70 to 80 ° C in a quencher (10).

Dabei werden wasserlösliche Stoffe und Stäube ausgewaschen und an in der Figur 1 mit Bezugzeichen (11) dargestellten Stelle abgeführt.This water-soluble substances and dusts are washed out and in the FIG. 1 removed with reference numeral (11) shown passage.

Daran anschließend wird das Rauchgas (II) zunächst einem sauer betriebenen Rotationswäscher (12) zugeführt, in welchem eine saure Waschflüssigkeit auf Schleuderräder aufgegeben wird, die einen feinen Flüssigkeitsnebel erzeugen. Beim Durchströmen dieses Nebels kommt das Rauchgas (II) in engen Kontakt mit der Waschflüssigkeit, so dass hier weitere saure Rauchgasbestandteile und auch Feinstäube ausgewaschen und abgeschieden werden.Subsequently, the flue gas (II) is first fed to an acidic rotary scrubber (12), in which an acidic scrubbing liquid is applied to spinner wheels, which produce a fine mist of liquid. As it flows through this mist, the flue gas (II) comes into close contact with the scrubbing liquid, so that further acid flue gas components and also fine dust are washed out and separated.

In ähnlicher Weise wirkt der dem sauer betriebenen Rotationswäscher (12) nachgeschaltete alkalisch betriebene Rotationswäscher (13). In dieser Stufe wird eine alkalische Waschflüssigkeit, im Ausführungsbeispiel mit Natronlauge versetzt, zugegeben, um restliche saure Rauchgasinhaltsstoffe zu entfernen.Similarly, the acid-operated rotary scrubber (12) downstream of alkaline-operated rotary scrubber (13) acts. In this stage, an alkaline washing liquid, in the exemplary embodiment mixed with sodium hydroxide added to remove residual acidic flue gas ingredients.

Die wenigen noch im Rauchgas (II) befindlichen festen oder flüssigen Schwebstoffe werden in einem elektrostatisch betriebenen Kondensationsfilter (14) abgeschieden. Das so behandelte Rauchgas (II) wird im Folgenden einer katalytischen Nachreinigung (15) zugeführt und anschließend als gereinigte Abluft über den Kamin (16) abgegeben.The few remaining in the flue gas (II) solid or liquid suspended matter are deposited in an electrostatically operated condensation filter (14). The flue gas (II) treated in this way is subsequently fed to a catalytic secondary purification (15) and then discharged as purified exhaust air via the chimney (16).

Verfahrensrelevante Parameter des AnwendungsbeispielsProcess-relevant parameters of the application example

1.1. 50 kg/h50 kg / h Stützbrennstoff im DrehrohrSupport fuel in the rotary tube 2.Second 135 t135 t Metallhaltiger Abfall (trocken)Metal-containing waste (dry) 3.Third 700°C - 850°C700 ° C - 850 ° C Rauchgastemperatur am Austritt des DrehrohresFlue gas temperature at the outlet of the rotary tube 4.4th 10-20 Uph10-20 Uph Drehgeschwindigkeitrotation speed 5.5th 79 t79 t ausgebrannter metallhaltiger Rückstand (trocken) (Verluste an rück zu gewinnenden Metallen ca. 1% gegenüber 10 % im Stand der Technik)burned-out metal-containing residue (dry) (losses of recoverable metals approx. 1% compared to 10% in the prior art) 6.6th 640 kg640 kg Staubdust 7.7th 1050 °C1050 ° C Rauchgastemperatur am Austritt der NachbrennkammerFlue gas temperature at the outlet of the afterburning chamber 8.8th. 30.000 Nm3/h30,000 Nm 3 / h RauchgasmengeSmoke gas volume

Die ausgetragenen Metallkonglomerate sind in Fig. 3 zu erkennen.The discharged metal conglomerates are in Fig. 3 to recognize.

Claims (15)

  1. Process for recovering metals from metal-containing wastes and/or materials, characterized in that the metal-containing waste and/or the material is introduced into a rotary tube furnace (1), treated thermally with continuous intensive mixing and oxidatively with addition of oxygen-containing gases, the organic components remaining in gaseous form are continuously removed and subsequently oxidized further and the metal-containing components are discharged from the rotary tube furnace (1), characterized in that the combustion temperature in the rotary tube furnace (1) is kept in a range from 400 to 1100°C by means of temperature measurement means, temperature regulating means and temperature control means by addition of coolant through a coolant addition lance (4) which projects from the feed end (1') into the rotary tube furnace (1).
  2. Process according to Claim 1, characterized in that the metal-containing waste and/or the material is continuously introduced into the rotary tube furnace (1) and the metal-containing components and the inorganic components which do not contain metal are continuously discharged from the rotary tube furnace (1).
  3. Process according to Claim 1 or 2, characterized in that the metal-containing components are preferably discharged as metal conglomerates from the rotary tube furnace (1).
  4. Process according to any of Claims 1 to 3, characterized in that the combustion temperature (T) in the rotary tube furnace (1) is kept in the range from 500 to 900°C.
  5. Process according to one or more of Claims 1 to 4, characterized in that the rotary tube furnace (1) is inclined to the horizontal.
  6. Process according to one or more of Claims 1 to 5, characterized in that the metal-containing waste and/or the material is transported from the feed end (1') to the outlet end (1") of the rotary tube furnace (1), with the waste firstly being heated in a heating zone (A), if appropriate with the aid of an auxiliary firing (3), the organic components then being thermally separated from the metallic components and at least partly, preferably mostly, burnt in a subsequent combustion zone (B) and the nonvolatile metal constituents together with any nonvolatile inorganic constituents present finally being discharged essentially continuously at the outlet end located opposite the feed end of the rotary tube furnace (1).
  7. Process according to one or more of Claims 1 to 6, characterized in that the components leaving the rotary tube furnace (1) in gaseous form are fed into an after-combustion chamber (7) which is located downstream of the rotary tube furnace (1) and in which complete oxidation of all residual organic compounds still present occurs and the residence time of the flue gas (II) is > 2 s and the temperature within the after-combustion chamber (7) is above 850°C.
  8. Process according to one or more of Claims 1 to 7, characterized in that the flue gas (II) laden with inorganic pollutants is purified in a number of stages to achieve low emission values.
  9. Process according to one or more of Claims 1 to 8, characterized in that the metal-containing waste is preferably electronics scrap which is comminuted or uncomminuted or these are deliberately added to the waste.
  10. Process according to one or more of Claims 1 to 9, characterized in that the combustion temperature (T) in the rotary tube furnace (1) is kept in a range in which, firstly, the burn-out of the waste to be treated is essentially complete and, secondly, the loss of metals to be recovered via the flue gas (II) is very low by means of temperature measurement means, temperature regulating means and temperature control means.
  11. Process according to one or more of Claims 1 to 10, characterized in that the temperature measurement means comprises an infrared camera (5) to determine the local temperature in the waste (17) to be treated within the rotary tube furnace (1).
  12. Process according to Claim 11, characterized in that the infrared camera (5) is located at the outlet end (1'') of the rotary tube furnace (1).
  13. Process according to any of Claims 1 to 12, characterized in that the flue gas (II) fed to the after-combustion chamber (7) is firstly treated thermally at temperatures above 850°C, dusts are precipitated in the downstream steam boiler (8) and collected in a dust chamber (9), the flue gas (II) is subsequently cooled to from 70 to 80°C by spraying in water in a quench (10), fed to a rotary scrubber (12) operated under acidic conditions in which an acidic scrubbing liquid is fed in onto rotary disks, fed to a rotary scrubber (13) operated under alkaline conditions, the solid or liquid suspended materials still present are precipitated in an electrostatically operated condensation filter (14) and the flue gas (II) is passed to a catalytic after-purification (15) and subsequently released as purified exhaust air via the chimney (16).
  14. Plant for the thermal treatment of metal-containing wastes and/or materials by a process according to one or more of Claims 1 to 13, characterized in that this plant comprises a rotary tube furnace (1), a continuously operating feed device (6), a coolant addition lance (4) which projects from the feed end (1') into the rotary tube furnace (1), at least one after-combustion chamber (7), at least one steam boiler (8), at least one quench (10), a rotary scrubber or at least two rotary scrubbers (12, 13) connected in series, at least one condensation electrofilter (11) and at least one catalytic after-purification (15) for the flue gases.
  15. Plant according to Claim 14, characterized in that the rotary tube furnace (1) is inclined in the horizontal.
EP20060724542 2005-05-06 2006-04-25 Method for recovering metals from waste and other materials comprising organic components Revoked EP1880028B8 (en)

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US11725256B2 (en) 2014-06-13 2023-08-15 Aurubis Ag Method for recovering metals from secondary materials and other materials comprising organic constituents
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US20090129996A1 (en) 2009-05-21
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WO2006119861A1 (en) 2006-11-16
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DE102005021656A1 (en) 2006-11-09
US7976611B2 (en) 2011-07-12

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